Vicinal-acryloxy-halo long chain compounds and process for same



United States Patent 3,304,315 VICINAL-ACRYLOXY-HALO LONG CHAIN COM- POUNDS AND PROCESS FOR SAME Charles S. Nevin, Decatur, Ill., assignor to A. E. Staley Manufacturing Company, Decatur, Ill., a corporation of Delaware No Drawing. Filed Jan. 18, 1962, Ser. No. 167,154 30 Claims. (Cl. 260404.8)

This invention relates to the preparation of vicinal acryloxy-halo long-chain aliphatic compounds. More specifically, this invention relates to the preparation of long-chain vicinal 'acryloxy-halo compounds by the reaction of an acid acrylic compound and an alkyl hypohalite with a long-chain unsaturated compound, i.e., a haloacylation reaction in which a halogen and an acyloxy group are introduced in one reaction on adjacent carbon atoms.

Various references, such as United States Patent 2,054,814 to Harford, United States Patent 2,514,672 to Reynolds et al., United States Patent 2,511,870 to Oroshnick and United States Patent 2,947,766 to Riener et al. disclose the haloacylation of unsaturated compounds, such as isoprene, acrylate esters and fatty acid esters, with an alkyl hypohalite and a saturated carboxylic acid. However, none of these references discloses such a reaction wherein an ethylenically unsaturated carboxylic acid is used as the acylating agent. This is not surprising since the double bond in an unsaturated carboxylic acid is the logical reaction site for the alkyl hypohalite and another molecule of unsaturated carboxylic acid. For example, if oleic acid was substituted for a saturated acid in the process of Reynolds et al., the majority of the haloacylation would take place at the double bond of the oleic acid (i.e., one molecule of oleic acid and one molecule of alkyl hypohalite would attack a double bond of a second molecule of oleic acid) and relatively little of the alkyl acrylate would take part in the reaction.

I have now found that the ethylenic double bond in an acid acrylic compound (i.e., alpha, beta-ethylenically unsaturated monocarboxylic acid or a half-ester of an alpha, beta-ethylenically unsatuarted dicarboxylic acid) is exceptionally resistant to haloacylation. In the presence of long-chain ethylenically unsaturated compounds, the electrophilic nature of the carboxy group of the alpha, beta-ethylenically unsaturated monocarboxylic acid and the presence of two such electrophilic groups in the halfesters of alpha, beta-ethylenically unsaturated dicarboxylic acids renders the ethylenic double bond in these acid acrylic compounds surprisingly resistant to attack by alkyl hypohalites. These acid acrylic compounds having this property can be represented by the formula H R1( 3=O Rr-ii-OH wherein R is hydrogen or 0 ll 00Y when R is hydrogen, R is hydrogen, alkyl of from 1 to 4 carbon atoms, alkoxy of from 1 to 4 carbon atoms, halogen, phenyl, benzyl, or

ice

R is hydrogen, halogen or alkyl of from 1 to 4 carbon atoms; and Y is an aliphatic or aromatic monovalent radical of up to 18 carbon atoms. The long chain ethylenically unsaturated compounds can be represented by the formula RCH CH=CHCH R; wherein is an aliphatic open chain of from 10 to 24 carbon atoms; and R is hydrogen or a monovalent aliphatic group.

One principal object of this invention is to provide a process of making novel vicinal acryloxy-halo aliphatic reaction products, which comprises reacting a long-chain ethylenically unsaturated compound, an acid acrylic compound and an alkyl hypohalite. Another principal object of this invention is the provision of novel acryloxy-halo long-chain aliphatic reaction products, which have utility in the preparation of useful resinous homopolymers and/ or copolymers. Another, and somewhat more general object of this invention is a process of making vicinal acryloxy-halo aliphatic compounds, which comprises reacting an alkyl hypohalite, an acid acrylic compound and an ethylenically unsaturated compound.

In one aspect, this invention is a process of reacting an alkyl hypohalite, an acid acrylic compound and a longchain ethylenically unsaturated compound to introduce halogen and an acyloxy group in one reaction on adjacent carbon atoms.

The half-esters of alpha, beta-ethylenically unsaturated alpha, beta-dicarboxylic acids are not articles of commerce since they undergo dismutation whereby a mixture of diester and free dicarboxylic acid forms within a short time after their preparation. The only commercially feasible method of preparing these compounds in good yields is to react a monohydroxy compound and the anhydride of the dicarboxylic acid. Since fumaric acid by its very nature cannot exist as an anhydride, its halfester cannot be prepared in this manner. This is a serious problem since the products of this invention that are based on the fumaric acid half-esters are among the most important commercially. Accordingly, an important object of this invention is a commercially feasible method of preparing acryloXy-halo long-chain aliphatic compounds, wherein the acryloxy group is the residue of a half-ester of fumaric acid. In a second aspect, this invention is a process of reacting a monohydroxy organic compound with maleic anhydricle to form a half-ester, isomerizing the maleic acid half-ester to a fumaric acid half-ester and then reacting the fumaric acid half-ester, an alkyl hypohalite and a long-chain ethylenically unsaturated compound.

REACTION MECHANISM AND PRODUCTS The products of this invention are prepared by reacting an acid acrylic compound (as defined above), an ethylenically unsaturated long-chain aliphatic compound (as defined above) and an alkyl hypohalite. The predominant reaction is the addition of the halogen atom of the hypohalite to one carbon atom of the C=C segment of the long-chain compound, apparently yielding a positive carbonium ion. The carbonium ion then seemingly attracts the negative anion of the acid acrylic compound to form a vicinal acryloXy-halo compound. The alkoXy anion, from the alkyl hypohalite, and the hydrogen ion of the acid acrylic compound combine to form an alkanol as a by-product. 'For example:

wherein R, R and R are as defined above; R is alkyl and X is halogen.

While the above equation shows the formation of a single compound, an isomeric mixture is commonly obtained, since the positive halogen ion can add to either carbon atom of the ethylenic group. The reaction also yields in minor proportions, lay-products which may be represented as follows, the notation being the same as before:

l UH-ORa and A typical distribution (approximate) of the products in the above reaction mixture is as follows: 65 mole percent acryloxy-haio derivative, 15 mole percentalkoxy-halo derivative (B), and 20 mole percent allylic-halo derivative (C). These reaction by-products are compatible with the halo-acryloxy reaction product and plasticize the polymers thereof.

Complex mixtures of the vicinal ,acryloxy-halo compounds are obtained particularly when poly-unsaturated compounds are reacted with less than an equivalent proportion of acid acrylic compound. Different numbers of acryloxy groups are attached to the starting compounds, and position isomers are also obtained. Accordingly, quite complex mixtures of reaction products are obtained, for example, from soybean oil having an average of 4- ethyleuically unsaturated groups per triglyceride molecule.

As pointed out above, the acylating acid acrylic compounds of this invention all have an ethylenically unsaturated double bond, which is itself a theoretical point of haloacylation. However, I have found that this ethylenically unsaturated double bond is quite stable in the presence of a long-chain ethylenically unsaturated compound. In the case of acrylic acid itself, and methacrylic acid as well, this resistance seems to be due in part to the terminal position of the ethylenic double bond, but more importantly to the presence of an electrophilic carboxyl group attached to a carbon atom of the ethylenic group, which makes the ethylenic double bond part of a conjugated double bond system. Alpha-chloroacrylic acid and the half-esters of maleic and furnaric acid are even less prone to undergo haloacylation because of the presence of a second electrophilic group on one of the carbon atoms of the ethylenic group. Any small amount of reaction between the acid acrylic compound and another molecule of acid acrylic compound yields product that is compatible with the main reaction products and polymers thereof or in most cases may be removed in an alkaline wash.

THE REACTANTS The hypohalite reactant While various alkyl hypohalites can be used in the instant invention for the haloacylatio-n reaction, tertiary alkyl hypoha-lites, such as tertiary butyl hypochlorite and tertiary amyl hypochlorite, are preferred, since they are considerably more stable than the normal and secondary alkyl hypohalites. For example, tertiary butyl hypochlorite can be distilled at about 79 C.; or further, even without distillation, it can be stored (in the dark) at room temperature for months Without decomposing. Further, the large size of the tertiary alkyl group ste-rically hinders the addition of the al'koxy group to the positive carbonium ion. Tertiary butyl hypoch-lorite is particularly adv-antageous because it can be produced easily and inexpensively.

The long-chain unsaturated reactant In somewhat greater detail the monovalent aliphatic group R of the long-chain ethylenically unsaturated compound can contain various other groups such as hydroxyl groups, carboxyl groups, carboxyl'ate groups, carbamyl groups, amino groups, nitrilo groups, car-bamato groups, halo groups, acy-loxy groups, mercapto groups, alkoxy groups, aryloxy groups, etc. The preferred long-chain ethylenically unsaturated compounds of this invention are the readily available, naturally occurring glyceride oils (which are considered as having carboxy'late groups), such as soybean, corn oil, cottonseed oil, hempseed oil, tung oi-l, safiiower oil, peanut oil, linseed oil, tobacco seed oil, cod oi-l, hearing (or menhaden) oil, castor oil, etc. Esters of other unsaturated long-chain acids are also advantageous as starting materials, such as the methyl ester of oleic acid, the 2-ethylhexyl ester of linoleic acid, various esters of tall oil fatty acids, etc. The glycerides and other esters generally are stable in the reaction of this invention although small proportions of secondary products (other than those previously mentioned) may be produced during the reaction in accordance with this invention.

On the other hand, the presence of groups in the longchain aliphatic compound that are reactive with the alkyl hypoha-lite, such as nitrilo o-r amino groups, or that are reactive with the car-bonium ion formed during the haloacylation, such as hydroxyl or carboxyl groups, can lead to other side reactions during the haloacylation reaction. In my experiments I have found that any side-reaction products of this type are compatible with the main reaction products and polymers thereof.

The following are representative of some others of the ethylenically unsaturated compounds, which can. be used in this invention:

4-decene; 9-octadecene; 9-tetracosene;

IO-hydroxydecene-Z; 1-hydroxyoctadecene 9; 6-hydroxytetracosene-9; 1-chloro-decene-4; l-bromoctadecene-Q; 1-chlorotetr-acosene-9; 1-nitril0decene-4; 1-nitrilooctadecene-4; 1-nitrilotetracosene-9; 1-aminodecene-4; 1-methylaminooctadecene-9; 1-dioctylaminotetracosene-9; 1-ca-rbamy1decene-4; N-ethyl-1-carbamylootadecene-9; N-dioctyl-1-ca|rbamyltetracosene-9;

When R in the preceding formula is substituted by a carboxylate group, the substituent can be represented by the formula:

wherein Z is the residue of a hydroxyl compound, in is a number ranging from 0 to 5, n is a number ranging from 0 to 5, the sum of m and n+1 is 1 to 6, the number of hydroxyl groups in the original hydroxyl compound, and each R is independently a group selected from the group consisting of hydrogen, monovalent aliphatic groups having from 1 to 24 carbon atoms and monovalent aromatic groups having from 6 to 18 carbon atoms.

The alcohols from which Z in the preceding formula may be derived can contain from 1 to 6 hydroxyl groups and from 1 to 24,carbon atoms. They can be saturated or ethylenically unsaturated. They may be open chain compounds such as n-butanol, glycerol, and sorbitol, or cyclic compounds such as furfury-l alcohols, cyclohexanol, and inositol. Among the suitable alcohols for this purpose are the monohydric alcohols ranging from methyl to lignoceryl, including the isomers in which the hydroxyl groups may be primary, secondary, or tertiary. Among the many suitable dihydric alcohols are ethylene glycol, trimethylene glycol, and the polyoxyalkylene glycols in which the oxyalkylene groups have 1 to 3 carbon atoms, i.e., the polymethylene glycols, the polyethylene glycols and the polypropylene glycols. Additional suitable higher polyhydric alcohols are pentaerythritol, arabitol, mannitol, tr-imethylol propane, trimethylol ethane, trimethylol methane, etc.

Suitable esters may also be obtained from aromatic hydroxy compounds such as phenol, the cresols, resorcinol, hydroquinone, naphthol, etc.

Included in the present invention are those compounds wherein the ester consists of a polyhydric alcohol only partially esterfield with a long-chain carboxylic acid, e.g. monoglycerides and diglycerides. Also included in the invention are esters of a polyhydric alcohol, acylated in part by saturated acids. For example, the glyceryl hydroxy groups in the foregoing monoglycerides and diglycerides may be esterified with acids such as acetic acid, benzoic acid, stearic acid, etc.

The acid acrylic compound The following compounds are representative of the various acid acrylic compounds, which can be used as acylating agents in this invention: acrylic acid; methacrylic acid; ethacrylic acid; alpha-chloroacrylic acid; alphabromoacrylic acid; alpha-iodoacrylic acid; alpha-phenylacrylic acid; alpha-benzylacrylic acid; alpha-propoxyacrylic acid; methyl hydrogen itaconate; methyl hydrogen maleate; methyl hydrogen fumarate; methyl hydrogen mesaconate; methyl hydrogen citraconate; ethyl hydrogen maleate; ethyl hydrogen fumarate; n-propyl hydrogen maleate; isopropyl hydrogen fumarate; n-butyl hydrogen maleate; tertiary-butyl hydrogen fumarate; isoa-myl hydrogen fumarate; 4-methyl-2-pentyl hydrogen fumarate; n-octyl hydrogen maleate; 2-ethylhexyl hydrogen fumarate; decyl hydrogen fumarate; lauryl hydrogen maleate; n-tridecyl hydrogen maleate; stearyl hydrogen fumarate; octydecyl hydrogen maleate; phenyl hydrogen maleate; p-cresyl hydrogen fumarate; benzyl hydrogen maleate; naphthyl hydrogen fumarate; ethyl hydrogen chlorofumarate; cyclohexyl hydrogen maleate; p-cresyl hydrogen maleate; p-ohlorophenyl hydrogen maleate; ethoxyethyl (Cellosolve) hydrogen fumarate; p-decylphenyl hydrogen maleate; allyl hydrogen maleate; etc.

Half-esters of alpha, beta-ethylenically unsaturated dicarboxylic acids An important characteristic of the half-esters of the unsubstituted alpha, beta-ethylenically unsaturated alpha, beta-dicarboxylic acids (maleic acid and fumaric acid) is that the properties of the acryloxy-halo polymerizable products based on these half-esters can be readily and inexpensively varied by selecting the proper alcohol from which the half-ester is made. For example, when the half-ester is based on a lower alcohol, such as isopropanol, copolymerization products of the compounds of this invention with monomers such as styrene, are more rigid than when the half-ester is based on a higher alcohol, such as Z-ethylhexanol. As a rule, the flexibility of the copolymers increases as the number of carbon atoms in the alcohol increases. Generally, aryl half-esters form harder, copolymerization products than the corresponding alkyl half-esters. Further, the half-ester-derived haloacryloxy compounds of this invention are frequently as cheap or cheaper than the acrylic acid-and methacrylic acid-derived compounds of this invention. In fact, products based on the isopropyl half-ester of fumaric or maleic acid have a decided cost advantage over the monocarboxylic acid acrylic compounds. While the halfesters of substituted alpha, beta-ethylenically unsaturated alpha, betadicarboxylic acids and the half-ester of itaconic acid offer the same product flexibility as the maleate and fumarate half-esters, the cost makes their use less attractive.

As pointed out earlier, the halo-acryloxy compounds based on the fumaric acid half-esters are an important class of polymerizable compounds of this invention. This is particularly true of the alkyl hydrogen fumarates having from 2 to 13 carbon atoms in the alkyl group. For some unexplained reasons the copolymers based on the fumarate half-esters are clearer, tougher, and have higher tensile strength than the corresponding products based on the maleate half-esters.

Preparation of fumarate half-esters The fumaric acid half-esters are prepared by reacting substantially equal molar quantities of maleic anhydride and a monohydric alcohol at a temperature of from about 20 C. to about 200 C., and isomerizing the maleic acid half-ester to the fumaric acid half-ester using heat and/or an isomerization catalyst.

In performing the esterification with maleic anhydride, various esterification catalysts, such as 3P p-toluenesulfonic acid, etc., can be used to catalyze the formation of the maleic acid half-ester. However, it is preferable to avoid using these catalysts since they prevent the orderly formation of half-esters by promoting the reaction of the free-acid group of the half-ester with the hydroxy compound, thereby increasing the yield of diester and dicarboxylic acid. Accordingly, the esterification-reaction product from maleic anhydride contains a mixture of diester, monoester, dicarboxylic acid (both maleic and fumaric) and possibly some unreacted anhvdride.

The presence of unreactive maleic diester can be tolerated as it only adds to the cost of the final product. However, free maleic anhydride, or free dicarboxylic acid, in the reaction mixture raises a serious problem, since these compounds can cross-link prematurely materials having more than one ethylenically unsaturated group per molecule into an infusible mass, (Where there is only one ethylenically unsaturated group per molecule, free maleic anhydride or dicarboxylic acid raises no problem. Further, fumaric acid which is also present is so inert and insoluble, and has such a high melting point that it often precipitates from the monomeric reaction product and/ or final polymer masses made from it.) Accordingly, when reacting a polyunsaturated compound with the half-ester, free dicarboxylic acid'or anhydride in the half-ester reaction product can be tolerated only in very small vantageously employed.

amounts, and it is desirable to keep the proportion to a minimum. Therefore, when an esterification catalyst of the above type is used in the preparation of the half-ester, it is preferred to use an excess of monohydroxy com pound and/or to separate the half-ester from any anhydride or dicarboxylic acid formed during esterification.

The half-ester can be prepared directly from the cis or trans dicarboxylic acid or the acid halide, and, in this case, the aforementioned esterification catalysts are ad- In this case too, the esterification-reaction product will usually contain a mixture of all the compounds that can occur with the maleic anhydride and an esterification catalyst and the same precautions should be observed.

For the foregoing reasons and because the initial reaction .product of equimolar proportions of anhydride and monohydroxy compound in the absence of a catalyst is the half-ester in almost quantitative yield, this is the preferred route.

Although the monohydroxy compound and maleic anhydride are preferably used in substantially equal molar proportions, it is possible to use either compound in excess. However, when maleic anhydride is used in a molar excess of 25% or more over the monohydroxy compound (i.e., a ratio of more than 1.0 to 0.8), the half-ester should be isolated from the reaction mixture before reacting it with a polyunsaturated compound, since any dicarboxylic acid formed from the unreacted anhydride can cross-link the polyunsaturated compound into an infusible mass, as pointed out previously. On the other hand, alcohols can be used in a substantial excess (e.g., 3 or 4 moles to 1 mole anhydride), provided no esterification catalyst is present. However, the free excess alcohol should be removed prior to the haloacylation, since, if it is not removed, it will compete with the acid acrylic compound in its reaction with the carbonium ion, thereby decreasing the yield of acryloxyhalo groups. When an esterification catalyst is present, the mole ratio of alcohol to anhydride should be no more than 1.5 to l. Aromatic hydroxy compounds, such as phenol or cresol, should not be used in an excess unless the unreacted hydroxy compound is removed, since any unreacted portion of these aromatic hydroxy compounds can inhibit the subsequent copolymerization of their monomeric haloacylation reaction prod- -ucts.

The half-esters can be prepared at a temperature of from about 20 C to 200 C. However, it is usually preferable to carry out this reaction at moderately elevated temperatures (e.g., 80 C.150 C.) in order to get a rapid reaction Without having the half-ester undergo dismutation (i.e., forming diester and dicarboxylic acid).

As the reaction temperature increases, the possibility of is used, and with such a catalyst the half-ester of maleic acid can be rapidly converted to the half-ester of fumaric acid at a temperature of from 50 C. to 150 C. without any significant dismutation. At temperatures as low as 80 to 110 C., the isomerization is complete in from about 5 to 60 minutes.

The following compounds can be used as isomerization catalysts: phosphorus oxychloride, phosphorus trichloride, thionyl chloride, phosphorus oxybromide, phosphorus oxyiodide, phosphorus oxyfluoride, phosphorus tribromide, phosphorus triiodide, phosphorus trifluoride, Z-ethylhexyl phosphoryl dichloride, di (2 ethylhexyl) phosphoryl rnonochloride, phosphorus thiobromide, phosphorus thiochloride, thionyl bromide, thionyl fluoride, hexadecane, sulfone chloride, toluene sulfone chloride, chlorosulfonic acid, sulfur monobromide, sulfur monochloride, sulfur dichloride, sulfuryl chloride, iodine, bromine, aluminum chloride, diethyl amine, sulfur dioxide, zinc hydrosulfite, etc. These catalysts can be used in an amount equal to from 0.0001 mole to 0.1 mole per mole of half-ester. Larger concentrations only increase the cost of the product without assisting the reaction. Thionyl chloride, aluminum chloride, phosphorus trichloride and phosphorus oxychloride are the preferred catalysts because of their availability and efiiciency.

When desired, it is possible to isomerize the maleate groups to fumarate groups after the haloacylation reaction. In these cases heat and/or isomerization catalysts are employed in the same manner as when the half-ester is isomerized, with the exception that the temperature used need only be less than the decomposition temperature of the reaction product. However, it is usually preferable to isomerize before the haloacylation reaction, since for some unexplained reasons monomers produced in this way copolymerize with vinylidene compounds to form products having higher tensile strength than corresponding copolymerization products of monomers isomerized after haloacylation.

Temperature and optional catalyst for the haloacylation reaction Vicinal acyloxy-halo compounds of this invention are prepared by reacting the acid acrylic compound, a longchain ethylenically unsaturated compound, and the .alkyl hypohalite at a temperature of from about -50 C. to about C. The reaction is strongly exothermic and the reaction mixture, particularly in large scale operations, should be cooled to prevent damaging temperature rise. Useful reaction rates without objectionable product discoloration and without decomposition are obtained in the range of 0-100 C. and the preferred range is about 25 -75 C. At 25 -75 C., the reaction is substantially complete in 1-5 hours, the vapor pressure of the preferred hypohalite (tertiary butyl hypochlorite) is moderate, product discoloration is nil, and side reactions of the acid arcylic compound with tertiary alkyl hypochlorite is suppressed. Higher reaction temperatures lead to product discoloration and to problems stemming from higher vapor pressure of the hypochlorite necessitating the use of pressure vessels. The chief disadvantage of lower temperatures is reduced reaction rate and correspondingly longer reaction time. In the preferred temperature range, useful products are obtained in %8 hours. Over the broader temperature range of -50 C. to 150 C., the reaction time will vary from virtually instantaneous reaction to reaction of several weeks duration.

Generally, when low temperatures are employed or a more rapid reaction desired, a catalyst, such as a tetraalkyl ammonium salt or a tetraalkyl phosphonium salt can be employed. Generally, these catalysts can be employed in a concentration of 0.0001 to 0.1 mole per equivalent of ethylenic unsaturation in the ethylenically unsaturated compound. Tetramethyl ammonium chloride is particularly efiicacious.

Proportions in the haloacylatio-n reaction The acid acrylic compound, alkyl hypohalite and long chain ethylenically unsaturated compound can be present in the reaction mixture in virtually any proportions. However, I prefer to use about one mole of alkyl hypohalite for each equivalent of ethylenic unsatnration in the ethylenically unsaturate compound. A higher proportion of the alkyl hypohalite accelerates the reaction only slightly and may create the inconvenience of having to remove excess hypohalite and/or alcoholic by-products' from the reaction product. However, this inconvenience may be compensated for the copolymers of the reaction product having increased toughness and/ or rigidity. For example, copolymers of styrene with the reaction product of tertiary butyl hypochlorite, soybean oil and acrylic acid in a ratio of 1.20:1.00:1.35 are stronger and more rigid than when the ratio is 1.00: 1.00: 1.35. Of course, a lower proportion of the alkyl hypohalite reduces the number of ethylenic groups that are haloacylated. However, useful products are obtained over the range of about 0.1 to about 3 moles of alkyl hypohalite per equivalent of ethylenic unsaturation.

When it is desirable to haloacylate as many of the ethylenic double bonds in the ethylenically unsaturated compound as possible, the acid acrylic compound should be used in the preferred proportion of about 1.2 to 2 moles per equivalent of ethylenic unsaturation in the ethylenically unsaturated compound, and the most effective concentration varies with temperature. For example, at about 45 C., a ratio 1.7 to 1 is most effective, while at about 65 C., a ratio of 1.35 to 1 is most effective. Compared with results at a l to 1 ratio, the preferred proportions provide a significantly higher reaction rate and yield of acryloxy-halo compound. Higher ratios than 2 to 1 provide relatively little additional increase in reaction rate and product yield, and this is more than offset by the disadvantage of having to remove a larger amount of unreacted acid acrylic compound from the reaction mixture or by the higher cost without corresponding advantage when the unreacted acid acrylic compound is left in the composition. Useful products, however, are obtained over the range of about 0.1 to about moles of acid acrylic compound per equivalent of ethylenic unsaturation in the ethylenically unsaturated compound. Al-

though it is not essential that the residual acid acrylic 4 compound be removed from the reaction mixture, it may be removed along with the alcoholic by-products by alkaline aqueous washing or by vacuum distillation.

A polymerization inhibitor, such as metallic copper, an amine, a phenolic or a quinoid compound, should be present in the haloacylation in the proportion of from about 0.001 to 0.5 weight percent of the reactants when an acid acrylic compound having terminal ethylenic unsaturation is employed as the acylating agent. Preferably the inhibitor should be used in the proportion of from about 0.01 to 0.1 weight percent of the reactants. Generally, the phenolic compounds are preferred since they have less tendency to produce undesirable color than the amines do; also the amines tend to react with alkyl hypohalites.

Further, sufiicient phenolic inhibitor is usually present in the commercially available monocarboxylic acids, and in this event it is unnecessary to add additional inhibitor. Acid acrylic compounds having an esterified carboxyl group on the beta carbon atom (e.g. maleic acid halfesters and fumaric acid half-esters) do not require the presence of a polymerization inhibitor unless there is terminal unsaturation in one of the reactants.

UTILIZATION The physical and chemical characteristics of the novel vicinal acryloxy-halo-compound reaction products contemplated by this invention, and more particularly the polymers and resins derived therefrom, are capable of wide variation by selecting properly the reactants, i.e. the unsaturated compound and the acid acrylic compound, and the extent of .acylation. The reaction products of this invention may be polymerized through the ethylenic groups in the acylating acid with known catalysts, either ionic or free radical, to form useful homopolymers, or they may be polymerized with other vinylidene compounds to form useful copolymers. Among the other vinylidene monomers with which the acryloxy-halo-compound reaction products of this invention may be copolymerized are methyl methacrylate, ethyl acrylate, butyl methacrylate, stearyl acrylate, acrylic acid, methacrylic acid, styrene, alpha-methyl styrene, allyl alcohol, vinyl acetate, vinyl stearate, vinyl chloride, vinylidene chloride, acrylamide, acrylonitrile, butadiene, etc. The acryloxy- -halo products of this invention may also be copolymerized with a wide variety of monomers having internal ethylenic unsaturation, using conventional catalysts and polymerizing conditions, to yield useful copolymers. Among such compounds are maleic anhydride, crotonic acid, cinnamic acid, dipentene, myrcene, etc. The copolyme-rs thus produced range from viscous liquids through soft gels to tough rubbery products and hard resins. The polymers (i.e., the homopolymers and copolymers) are useful broadly in the manufacture of cast, molded and extruded forms, as fiber-reinforced laminating and molding resins, as surface coatings, adhesives, plasticizers, and as paper and textile treating agents.

The products of this invention are useful broadly in the production of homopolymers and copolymers. T-he methacryloxy and acryloxy compounds are photo-sensitive and must be stored in the dark to prevent premature polymerization. In the absence of light, they are stable for months at room temperature. To prevent deterioration because of labile halogen, the stored acryloxy-halo monomers should contain about 0.05 percent to 5 percent by weight of a stabilizer such as barium-cadmium soap, epoxidized soybean oil, or a tin mercaptide. Virtually any of the stabilizers used for polyvinyl chloride, chlorinated polyethylene or polyolefins prepared with a Zieglertype catalyst can be incorporated in these products, just so the stabilizer does not prevent their subsequent polymerization.

Other variations in the process While the instant invention is primarily directed to the haloacylation of long chain ethylenically unsaturated compounds, it can also be used to introduce an acryloxy group into a wide variety of other ethylenically unsaturated compounds, such a ethylene, propylene, butene-l, -butene-2, hexene-l, heptene-3, diisobutylene, nonene-3, octadecene-l, butadiene, isoprene, tetramethylethylene, cyclohexene, cyclooctene, alpha-pinene styrene, alphamethyl styrene, p-methyl styrene, o-octyl styrene, 2,5-dichlorostyrene, vinyl chloride, vinyl bromide, allyl chloride, chloroprene, allyl alcohol, diallyloxypentaerythritol, vinyl acetate, vinyl propionate, vinyl stearate, methyl acrylate, stearyl methacrylate, acrylic acid, methacrylic acid, acrylonitrile, acrylamide, etc., or even natural rubber. As a general rule, those compounds, which contain an internal ethylenic double bond, such as cyclohexene or nonene-3, can be haloacylated under the same conditions as the preferred long-chain ethylenically unsaturated compounds of this invention. On the other hand those compounds which contain only terminal unsaturation, such as ethylene and propylene, require temperatures in excess of about 20 C. and/ or a haloacylation catalyst (e.g., tetramethyl ammonium chloride) since terminal ethylenic double bonds are somewhat harder to haloacylate than internal ethylenic double bonds. Those compounds, such as vinyl chloride and acrylic acid, itself, are still harder to haloacylate because of the presence of electrophilic groups in close association with the ethylenic double bond. Generally, the larger the number of electrophilic groups in close association with the ethylenic double bond, the harder it is to haloacylate the ethylenic double bond; usually these can only be haloacylated with the aid of a haloacylation catalyst at a temperature in excess of about 20 C.

As the reactivity of the ethylenically unsaturated compound toward haloacylation decreases, the tendency for the ethylenic double bond of the acid acrylic compound to be haloacylated increases and, accordingly, this by-product is formed in increased amount in the reaction product. This reaction product is compatible with the various other products formed during the haloacylation and the polymers thereof. However, the haloacylated acid acrylic compound can be extracted with alkali. As pointed out earlier, acylating acids such as chloroacrylic acid and the half-esters of maleic acid and fumaric acid are less susceptible to attack by alkyl hypohalite than acrylic acid itself, and methacrylic acid. Accordingly, the amount of the by-products formed by the haloacylation of the acylating acid can be controlled by the choice of acylating acid.

These compounds form interesting and useful copolymerizable and/ or homopolymeriza ble monomers. The products based on ethylene and propylene are particularly interesting, since these haloalkyl esters of an acid acrylic compound can be readily converted to corresponding aminoalkyl esters and/ or unsaturated esters having unsaturation in both the alcohol and acid portion of the ester.

The following examples are merely illustrative and should not be construed as limiting the scope of the invention. In the examples meq. refers to milliequivalents.

Example I One hundred and seventy-four grams (2 moles) of methacrylic acid containing 0.025 percent by weight pmethoxy phenol and 204 grams of soybean oil (1.00 equivalent of ethylenic unsaturation) were weighed into a Morton flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel with an inlet tube extending to the bottom of the flask. One hundred and twelve grams of 97 percent pure tertiary butyl hypochlorite (1.0 mole) was added gradually from the dropping funnel over a 15 minute period to the stirred reaction mixture, while cooling the reaction mixture to hold its temperature at 40 C. Stirring at the same temperature, with heating as required, was continued for 5 hours. A small sample of the product, which weighed a total of 490 grams, was put aside for analysis. The reaction mixture was diluted with an equal volume of hexane and repeatedly washed with 50 ml. portions of percent aqueous disodium phosphate until a test washing with distilled water showed no residual free acid. The alkaline washing also removed by-product tertiary butyl alcohol from the hexane solution of the reaction product. The hexane was then vacuum stripped off yielding 312 grams of a clear, light yellow oil.

The samples, which are identified as A, the untreated reaction product, and C, the alkali washed product, were analyzed for vinyl unsaturation, total unsaturation, chlorine and acidity. Total terminal unsaturation was determined by a near infrared absorption band method (NIR) as described by R. F. Goddur at page 1790 in volume 29- of Analytical Chemistry. The total ethylenic unsaturation was determined by the pyridine sulfate dibromide method described at page 203 of the 1954 edition of Monomeric Acrylic Esters" by E. H. Riddle.

TAB LE I 1 Not run.

From the above data it was calculated that 65.2 mole percent of the ethylem'c double bonds in the soybean oil were now substituted with vicinal methacryloxy and chloro groups, mole percent of the ethylenic double bonds inthe soybean oil were allylic chloride groups and that 19.8 mole percent of the ethylenic double bonds in the soybean oil were now substituted with vicinal butoxy and chloro groups.

Example 11 Example I was repeated except that 1.7 mole of methacryli c was used instead of 2.0 mole and the reaction was run for 2 hours instead of 5 hours. Before the alkaline extraction was carried out, the sample was vacuum distilled at 25 mm. pressure and 50 C. in order to remove all the tertiary butyl alcohol and some of the unreacted methacrylic acid. This sample is identified as product B.

From the above data it was calculated that 72.2 mole percent of the ethylenic double bonds in the soybean oil had vicinal methacryloxy and chloro su'bstituents, 8.8 mole percent of the ethylenic double bonds in the soybean oil were allylic chloride groups and that 19 mole percent of the ethylenic double bonds in the soybean oil had vicinal butoxy and chloro substituents.

Example III Example I was repeated except that acrylic acid was used instead of methacrylic acid. Sixty-one and ninetenths mole percent of the ethylenic double bonds in the soybean oil had vicinal acryloxy and chloro groups.

Example IV Example II was repeated except that acrylic acid was used in place of methacrylic acid and the reaction was carried out at 65 C. for 1.5 hours. Fifty-nine and seventenths mole percent of the ethylenic double bonds in the soybean oil were substituted with vicinal acryloxy and chloro groups.

Example V Ninety-six and four-tenths grams of acrylic acid (1.32 mole) containing 0.02 percent by weight p-methoxy phenol and 300 grams of soybean oil (1.50 equivalents of'ethylenic unsaturation) were weighed into a Morton flask equipped as described in Example 1. One hundred and sixty-eight grams of 97 percent pure tertiary butyl hypochlorite (1.5 mole) was added gradually from the dropping funnel over a 15 minute period to the stirred mixture, while cooling the reaction mixture to hold its temperature at 65-70 C. Stirring at the same temperature, with heating as required was continued for minutes. A total of one hundred and twenty grams of tertiary butyl alcohol and unreacted acrylic acid was vacuum distilled off at 50 mm. pressure. The remaining 444 grams of product was copolymerized with 30 percent by weight styrene using 1 percent by weight benzoyl peroxide.

Example V1 Example V was repeated except that 1.13 moles of acrylic acid was reacted for 65 minutes instead of 1.32 moles of acrylic acid.

Example VII 7 Example V was repeated except that 0.99 mole of acrylic acid and 1.13 moles tertiary butyl hypochlorite were reacted for 55 minutes instead of 1.32 moles of acrylic acid and 1.5 moles of tertiary butyl :hypochlorite.

13 14 TABLE III a second weighing disk, a 2 inch diameter circular mold was formed. Polymerization at 80 C. for 6 hours pro- Example Number duced a A; inch thick polymer casting. Example Example IX V VI VII 5 Example VIII was repeated except that the lsomeriza- Weight of sample before vacuum distillation, g. 564 545 503 non Step was Omltted' Weight ofresidue, g 444 442 42a icigigy beiore vacuum distillation, nne 0.87 0. 51 0. 63 Example X 3 2 8 gf ggf igfig 55 5,; The ethyl half-ester product was prepared using the vicinalaeryloxyand chloro groups 55.2 53 44.8 10 method and mole proportion of reactants of Example t;figgfgifigggfifi fgjgggggfjf{T 2L3 2L3 Q0 VHI except that the half-ester was isomerized at 80 C. Percent of eth lenic groups converted to for 10 minutes using 0.33 weight percent thionyl chloride. Tchlolroallyllcgl'lroufpsn..1 gfini 18.6 19.5 16.1

EH81 (3 S ren O O 'm V S 8119, p.s.i 1,970 1,860 580 Example XI 15 Example X was repeated except that the lsomerlza- The results of next ten examples are set forth in Step was Omltted' Table IV. Example XII I Example The isopropyl half-ester product was prepared using the One and one-half moles of maleic anhydride (147 mfithod and 111016 Proportion of Tea tant5 0f Example grams) was weighed into a flask equipped with a stirrer, except that h -Q Was {Someflled at f thermometer, condenser and dropping funnel, and then 9 for 30 minutes 1151118 Welght 'p thlonyl heated to 1105 C o d o h 1f moles f methanol chloride and the haloacylation was carried out at 40 C. (48 grams) was added slowly from the dropping funnel Over a 90 minute P while mlintaining the teni lperaturle of the reaction mixture Examp 1,; X111 at 90-1 0 When su Clem was i generated Example XI-I was repeated except that the isomerizaby the reaction, the external heating was discontinued and o tlon step was omitted. the temperature rose to l35-140 C. The reaction mixture was allowed to cool to 100 C. and maintained at Example XIV this temperature for 1 hour. An analytical sample of the The -P PY half-ester Product Was P p 115mg the reaction product had an acid value of 7.58 meq./ig. (them h nd m le pr portion of reactants of Example oretical 7.70 meq./g.) and a saponification value of 15.34 V I c pt t t f st r W215 isomer-ized at 90- meq./ g. (theoretical 15.40 meq./g.). lInfrared spectro- 100 C. for 10 minutes using 1.0 weight percent thionyl photometric analysis confirmed that the half-ester of male chloflde d the 'h l cyla ion Was Carried out at 55 C. ic acid had been prepared. Sixty-eight hundredths of a v r a 6 minute p ri dgram of l Cl (0.005 rnole) was added to the reaction mix- Example XV ture, while malntalnmg the reactants at 110 C. for 12 Th b t 1h If t d t d th minutes. Infrared analysis indicated that 95 percent of 3 er 2. He f g the maleic acid half-ester had been isomerizecl to fumarate m 0 an me e proper 0 i an s Xamp e hqlflester Groups 40 VIII except the half-ester was lsomerlzed at 85 C. for 15 (A) Twenty-six grams of the methyl hydrogen fumarate 2 g? 5 Welght g i Q 23? cchlomde gg (0.2 mole), 40 grams soybean oil (0.2 equivalent) and 9 y Z was came on a over a 0.01 wt. percent p-methoxyphenol were heated to 65 C. mmu e perm E l XVI in a Morton flask equipped as described before. xamp e Twenty-two and one half grams of tertiary butyl hypon ry butyl half-ester product was prepared chlorite (0.2 mole) was added gradually to the reaction using the method and molt? P QP P of Example VIII mixture, while cooling to maintain 65 C, Th reaction except that the half-ester was isomerlzed at 100 C. for was continued at this temperature f 0 minutes The 30 minutes using 028 Weight percent thionyl chloride and product Weighed 1105 grams the haloacylation was carried out at 45 C. over a 140 (B) A second sample Weighing 74.6 grams was preminute penodpared by the method of part (A) except that the volatiles Example XVII were removed by vacuum distillation at 50 mm. pres- The allyl half-ester product was prepared using the sure. method and proportions of reactants of Example VIII A portion of product (B) was mixed with 33 percent by except that the half-ester was isomerized at 90-100 C. weight styrene, 1 percent Advastab BC10-5 heat stabifor 30 minutes using 0.50 weight percent P01 as the isomlizer (a metal soap) and 1 percent benzoyl peroxide and erization catalyst and the haloacylation was carried out placed in an aluminum weighing cup. By covering with at C. over a minute period.

TABLE IV Percent of Ethylenie Percent Groups in Example Trans Weight of Sample Acidityinmeqjg. Oil Substi- Description of Polymer Isomer in Grams tuted With Casting Vicinal Acyloxy and Chloro A, 110.6; E, 74.6... A, 0.91; B, 1.31.--. 48.9 Cltearwllned. hard, flexible,

OLl 0 A, A, 0.90; B, 0.95.--. 64. 1 Cloudy, soft, flexible. A, A, 0.95; B, 1.04..-- 59.5 Med. soft, flexible.

0 A, A, 0.86; B, 0.99...- 53. 25 Cloudy, soft, flexible. 100 A, A, 1.01; B, 1.12.... 54. 9 Clear, hard, rigid, tough.

0 A, A, 0.91; B, 0.99.-.- 61.4 Cloudy, soft, flexible. 100 A, A, 1.04; B, 1.14..-. 50.8 Clear, hard, rigid, tough. 100 A, A, 1.02; B, 1.21.... 50. 3 Cloudy, soft weak.

98 A, A, 0.74; B, 0.81.-.- 35. 3 Clagbrired. hard, slightly 1 e. 100 A, A, 0.90; B, 1.05.--. 44. 0 Cloil dy, soft, weak, flexible.

15 The results of the next five examples are set forth in Table V.

Example XVIII One mole of maleic anhydride (98 grams) was weighed into a Morton flask equipped as before. One mole of methyl amyl alcohol (4-methyl-2-pentanol) (102 grams) was added slowly over 35 minutes from a dropping funnel while maintaining the reaction mixture at 110 C. Sixty-eight hundredths of a gram of PCl (0.005 mole) was added to the reaction mixture while maintaining the reactants at 110 C. for minutes. Immediately thereafter, two hundred grams of soybean oil (1.0 equivalent of ethylenic unsaturation) was added to the reaction mixture and the temperature of the reaction mixture was adjusted to 65 C. One hundred and twelve grams of 97 percent pure tertiary butyl hypochlorite (1.0 mole) was immediately added to the reaction mixture over a period of 20 minutes, while maintaining the reaction mixture at 65 C. The product was isolated by the method of Example VIII (B) and then copolymerized with 30 percent by weight styrene in the same manner.

Example XIX Example XVIII was repeated except 1.2 moles of methylamyl alcohol and 1.2 moles of maleic anhydride were used.

Example XX Example XVIII was repeated except that A of the methylamyl alcohol was replaced by A mole of isobutanol. 7

Example XXI The 2-ethylhexyl half-ester reaction product was prepared using the method and proportions of Example XVIII.

Example XXII using the method and proportions of Example XVIII.

methacrylic acid (0.425 mole) containing 0.025 percent by weight p-methoxy phenol and 27.1 g. of 99.6 percent tertiary butyl hypochlorite (0.25 mole) were reacted for 90 minutes at 65 C. The reaction mixture was stripped at 25 mm. pressure and 50 C. Acidity and infrared analysis showed 46.7 mole percent of the oil uns-aturation had methacryloxy and chloro substituents. Further analysis indicated that 14 mole percent of the oil unsaturation was al-lylic chloro groups and that 30 mole percent of the oil unsaturation had butoxy and chloro substituents. A copolymer with 33 percent by weight styrene was reddish brown, transparent, hard and brittle.

Example XXV Thirty-three and two-tenths grams of linseed oil (0.25 equivalent of ethylenic unsaturation) was used in place of the 0.25 equivalent of menhaden oil in Example XXIV. Fifty-seven and one-half mole percent of the ethylenic groups in the oil had methacryloxy and chloro substituents, 14.4 mole percent of the ethylenic groups in the oil were chloro allylic groups and 12 mole percent of the ethylenic groups in the oil had butoxy and chloro substituents. A copolymer with 33 percent by weight styrene was amber-colored, transparent, hard and rigid.

Example XXVI Thirty-one and five-tenths grams of tung oil (0.300 equivalent of ethylenic unsaturation) was mixed with 43.9 grams (0.510 mole) of methacrylic acid containing 0.025 percent p-methoxy phenol. This mixture was reacted with 32.6 grams (0.300 mole) of tertiary butyl hypochlorite for 90 minutes at 65 C. The reaction product was stripped at 25 mm. Hg and 50 C. to remove the t butyl alcohol by-product. Infrared spectrophotometric analyses showed 45.7 mole percent of the oil unsaturation was converted to vicinal methacryloxy-chloro substituents. A copolymer of the oil product containing 33 percent by weight styrene was clear, light yellow, quite hard and rigid.

TABLE V Percent of Ethylenie Groups in Oil Substituted with Tensile Percent Weight of Strength of Example Trans Sample Acidity in me /g. Polymer Isomer in Grams Acyloxy and Butoxy and Casting,

Chloro Chloro p.s.i.

100 A, 504; B, 437 A, 0.90; B, 0.90-.-. 50. 8 17. 7 383 100 A, 549; B, 481 A, 1.13; B, 1.25 50.8 8. 8 507 100 A, 502; B, 437 A, 0.87; B, 0.95 58.5 20.3 645 100 A, 532; B, 478 A, 0.83; B, 0.91. 56.4 17.4 100 A, 607; B, 544"- A, 0.75, B, 0.80-.-. 56. 5 33. 7 274 Example XXIII Four hundred'and fifty-three grams of castor oil (1.5 equivalents of ethylenic unsaturation), 220.8 grams of methacrylic acid (2.55 moles) containing 0.075 percent by weight p-methoxy phenol and 163.9 grams of 99 percent pure tertiary buty l hypochlorite (1.5 moles) were reacted for 90 minutes at C. The reaction mixture was stripped at 25 mm. and C. to remove the tertiary butyl alcohol by-product. Acidity and infrared spectrophotometric analysis of the sample showed 42.5 mole percent of the oil unsaturation was converted to the vicinal methacryloxy-chloro derivative. Further analysis indicated that 30 mole percent of the oil unsaturation was allylic chloro groups and that 22 mole percent of the oil unsaturation h-ad butoxy-chloro substituents.

The stripped product was copolymerized with 33 percent by weight styrene, using 1 percent benzoyl peroxide and 1 percent barium-cadmium carboxylate at 65 C. for 4 hours.

The cast sheet was yellow, slightly opaque, semi-hard .and slightly flexible.

.Example XXIV Thirty-six and one-fourth grams of menhaden oil (0.25 q ival n of' e hylenic unsaturation), 36.55 grams of Example XXVII Four hundred and forty-five grams of methyl oleate (1.5 equivalents of ethy-lenic unsaturation) was used in place of the 1.5 equivalents of castor oil in Example XXIII. Analysis of the product showed that 60 mole percent of. the ethylenically unsaturated groups in the ester had chloro and methacryloxy substituents. A copolymer with 33 percent by weight styrene, which had been cured at C. for 1 hour after the initial copolymerization at 65 C. for 3 hours, was a tough, quite flexible solid which adhered to the aluminum mold.

Example XX VIII thru XXX VI A series of tall oil esters were reacted with tertiary butyl hypochlorite and methacrylic acid containing 0.05 percent p-meth-oxy phenol at 45 C. using a concentration of 1.7 moles of methacrylic acid, 1.0 mole tertiary butyl hypochlorite and sufficient tall oil ester to contain 1.0 equivalent of ethylenic unsaturation. A portion of the sample was stripped at 50 C. and 50 mm. pressure and a second portion was alkali extracted by the method of Example I. Table VI lists the characteristics of the tall oil esters which were prepared by conventional esterification techniques. Table VII lists the characteristics of the haloacylated product and Table VIII lists the properties 1 7 of a copolymer of the vacuum stripped reaction product with 33 percent by weight styrene.

, 18 were mixed at room temperature. Tertiary amyl hypochlorite (27.2 g.=0.20 mole of 90 percent purity) was TABLE VI 'Iall Oil Acidity, Saponifi- Hydroxyl, Unsat- Ester Unsatura- Fatty Acid Ester meq./g. cation, meq./g. uration, Groups per tions per meq./g. meq./g. Molecule Molecule Benzyl 0. 03 2. 82 0.10 3. 74 1. 1. 32 Cyclohexyl 0. 07 2. 77 0. 13 3.94 1. 0 1. 42 Soybean fatty alcohol 0. 03 1. 93 0. 14 4. 96 1. 0 2. 57 2-ethylhexyl 0. 06 2. 55 3. 43 1. 0 1. 38 Pentaerythritol 0. 02 3. 35 4. 67 3. 4 5. 1 Sorbitol 0. 01 3. 29 0. 4. 71 4. 2 6. 0

2 1.36 equivalents in oil portion and 1.0 equivalents in allyl portion.

TABLE VII Percent Ethylenio Groups in Ester Which are Number of Tall Oil Fatty Weight of Sample Acidity, rneqJg. Acryloxy Acid Ester in Grams Groups per Acryloxy- Butoxy- Allylic- Molecule Chloro Chloro Chloro Benzyl A, 7658; B. 666.0; A, 2.03; B, 2.20; 55. 6 16. 3 13.0 0.73

Cyclohexyl A, 761.8; B, 687.0; A, 2.09; B, 2.26; 53.3 19.3 15. 9 0.75

Soy fatty alcohol A, 687.8; B, 590.0; A, 2.17; B, 2.37; 56.0 8.7 17. 2 1.44

2-ethylhexyl A, 685.2; B, 600.0; A, 2.01; B, 2.10; 54.7 13. 1 18. 4 0. 75

Peutaerythritolunc A, 705.0; B, 611.0; A, 2.23; B, 2.44; 59.7 10.3 15. 0 3.04

Sorbitol A, 702.8; B, 617.0; A, 2.15; B, 2.38; 55.0 17.3 15. 3 3.30

Ethylene A,C714.1; B, 604.0; A,C2.08; B, 2.28; 70.0 14.8 1.64

Furfuryl A, 406.0; C, A, 3.29; C, 0.53.... ea. 35 19.3 0.52

Allyl A, 52.4; B, 43.1 A, 2.18; B, 2.33 on. 60 29. 0 0.86

As in the preceding examples, A is the crude reaction product, B is the vacuum stripped product and C is the alkali washed product.

TABLE VIII Percent Free No. of Tall Oil Fatty Methacrylio Acryloxy Acid Ester Acid in Groups Polymer Properties Reaction per Fatty Mixture Molecule Benzyl 12.6 0. 73 Hard, tough, slightly flexible.

Oyclohexyl 12. 9 0. 75 Do.

Soybean Fatty 13. 6 1. 44 Rigid, tough, and hard.

Alcohol.

2 ethylhexyl 12.10 0. 75 Tough, flexible.

Pentaerythritol... 13. 3 3. 04 Rigid, tough, and hard.

Sorbito1 13. 6 3. 30 Do.

Ethylene 13. 1 1. 64 Hard. tough, and slightly flexible.

Furfuryl 13. 3 0. 52 Polymerized in 32 hours to an easily tearible flexible polymer.

Allyl 13. 3 0. 86 Tough, flexible.

Example XXXVII A commercially available soybean oil monoglyceride having 3.87 meq./ g. of ethylenic unsaturation was haloacylated using the same conditions and proportions employed in the preceding nine examples. The product had 33.7 mole percent acryloxy-chloro groups, 23.5 mole percent butoxychloro groups, 14.3 mole percent of the oil unsaturation were allylic chloro groups and 0.45 acryloxy groups per molecule. A copolyrner of the vacuum stripped product with 33 percent by weight styrene was hard, tough and slightly flexible.

Example XXXVIII This example illustrates the use of tertiary amyl hypochlorite. Soybean oil (40.0 g.=0.20 mole of unsaturation), methacrylic acid (17.2 g.=0.20 mole), and pmethoxy phenol (0.05 wt. percent of the methacrylic acid) Sample Sample Sample Acidity, meqJg. 1. 05 0. 18 0. 03 Saponitication, meqJg-.- 6. 06 6. 75 6. 63 Total chlorine, meqjg..- 2. 40 3. 05 3. 14 Allyllc chlorine, meqJg 0. 48 0. 61 0. 58 t-Arnyl Alcohol, wt. percent (by G.L. P.

Chromatography) 18. 7 0. 1 2. 5 Total Vinyl Unsaturation, meq./g. (by

Near Infrared Spectrophotometrwu 2. 27 1. 78 l. 65

Calculations, based on these analyses, show that the soybean oil was converted to the following products. The quantitative values are based on the moles of unsaturation in the original soybean oil.

Mole Percent Vicinal chloro-methacryloxy soy oil 55 Vicinal chloro-amyloxy soy oil 10 Allylic chlorinated soy oil 20 Chlorinated soy oil 15 p A small portion of the liquid B sample (9.90 g.) was mixed with styrene (4.95 g.) and benzoyl peroxide 19 (0.15 g.) and cast in a mold to form a A; inch thick sheet. The casting was heated at 65 C. for 16 hours followed by a post cure of 30 minutes at 120 C. The copolymer formed was a clear, pale yellow, solid. It had a Clash-Berg elastic modulus T value of 38 C. and a Barcol 935 hardness value of 45-30.

Example XXXIX This example illustrates the use of aluminum chloride as an isomerization catalyst. Maleic anhydride (98.0 g.E1.00 mole) was heated to 110 C. in a reaction vessel equipped with a stirrer, a condenser, and a reactant addition port. Methylamyl alcohol, i.e., 4-methyl-2- pentanol (102.0 g.=1.00 mole) was added over a 40 minute period while controlling the exothermic reaction at 110114 C. This reaction temperature was maintained for an additional 20 minutes, then the reaction mixture was cooled to 90 C. Aluminum trichloride (1.00 .50.0075 mole) was added and the temperature was controlled at 90 C. for 25 minutes. Soybean oil (200.0 g.E1.00 mole of unsaturation) and p methoxy phenol (0.03 g.z0.015 mole) was added rapidly and the temperature was adjusted to 65 C. Tertiary butyl hypochlorite (110.0 gELOO mole of 98.5 percent purity) was added over a period of 60 minutes while controlling the exothermic reaction at 65-70 C. This reaction temperature was maintained for an additional 30 minutes. The pressure was reduced to 25 mm. Hg and while maintaining 65-70 C., and mixing vigorously the tertiary butyl alcohol by-product was removed by distillation.

The product was a clear, pale-yellow liquid having a viscosity of 5000 c.p.s. at 25 C. Copolymerization with styrene yielded a flexible resin having a tensile strength of 500 p.s.i. and a Clash-Berg elastic modulus T value of 20 C.

Example XL Methacrylic acid (117 g.z1.35 mole) containing 0.025 percent p-methoxy phenol and soybean oil (200 g.1.00 mole of unsaturation) were mixed and heated to 65 C. Tertiary butyl hypochlorite (110 g.E1.00 mole of 98.5 percent purity) was added slowly over a period of 30 minutes While controlling the exothermic reaction at 65- 70 C. This reaction temperature was maintained for an additional 90 minutes. The pressure was reduced to 25 mm. Hg and while maintaining 65-70 C. and mixing vigorously the tertiary butyl alcohol by-product was removed by distillation.

The chemical and physical characteristics of the clear, pale-yellow liquid product was as follows:

Refractive index, n 1.4725 Brookfield viscosity, cp. at 25 C. 730

The soy oil product (66 parts) was combined with styrene (33 parts) and benzoyl peroxide (1 part), cast in a inch sheet, and cured 16 hours at 65 C. and 0.5 hour at 110 C. The copolymer had the following physical characteristics:

This example was repeated using a different ratio of reactants; methacrylic acid (56.5 g.E0.65 mole) containing 0.025 percent p-methoxy phenol, soybean oil (200 gELOO mole of unsaturation), and t-butyl hypochlorite (110 g.E1.00 mole of 98.5 percent purity).

The soy oil product copolymerized with 33 percent styrene had the following physical characteristlcsz Flexural modulus, p.s.i 28,600 Flexural strength, p.s.i 630 Tensile strength, p.s.i 1,390 Elastic modulus, Clash-Berg T C 29 Heat distortion, 66 p.s.i. C. 24 Shore hardness -93 Example X Ll A mixture of high purity heptene-3 (49.0 g.E0.50 mole), methacryrlic acid (43.3 g.z0.50 mole), and pmethoxy phenol (0.022 g.E0.05 percent of the methacrylic acid) was heated to 60 C. Tertiary butyl hypochlorite (54.5 g.z0.50 mole) was added slowly while maintaining the exothermic reaction at 65 C. by external cooling. After minutes at 65 C. the mixture gave a negative potassium iodide test for hypochlorite. A sample of the total reaction products was labeled A.

One half of the product was heated at 55 C. and the pressure was reduced to 12 mm. Hg. This removed most of the t-butyl alcohol by-product by distillation. The liquid residue was labeled sample B.

The remaining half of the total reaction products was dissolved in two volumes of ethyl ether. This ether solution was washed first with 8 percent aqueous Na HPO solution until alkaline and then with distilled water until slightly acidic (pH 5.5-6.0). Paramethoxy phenol (0.02 wt. percent of the product) was added and the ether solvent was removed by vacuum distillation at 65 C. and 25 mm. Hg. The liquid residue was labeled sample (C-9 The following table presents the analytical data obtained with the A and C samples:

Sample Sample A C Acidity, meq./g 1. ()2- O. 02 Saponification, rncq./g 6. 58 7. 87 Total Chlorine, meq./g 3. 46 5. 02 Allylic Chlorine, meqjg l 0. 31 0. 4.0 t-Butyl Alcohol, wt. percent (by G hromat-ography) 22. 8 2. 1 Total Vinyl Unsaturation, meq./g. (by Near Inhared spectrophotometry) 3. B9 3. 42 Total Unsaturation, meqJg. (by Catalytic Hydrogenation) 4. 38 4. 72

Calculations, based on these analyses, show that the heptene-3 was converted to the following products.

Mole percent Vicinal chloro-methacryloxy heptane 69 Vicinal chloro-butoxy heptane 9 Chlorinated heptene-3 18 A small portion of the B sample was mixed with 2 percent benzoin, cast in a cellophane mold, and exposed to ultraviolet light for 2 hours. It polymerized to a water clear, hard, rigid solid. A second portion of sample "B was copolymerized similarly with 30 percent styrene to form a pale yellow, hard, opaque, brittle solid. A small portion of the C sample was homopolymerized similarly to form a pale yellow, opaque, brittle solid which was harder than the B-homopolymer.

Example XLII This example illustrates the haloacylation of methacrylic with a second methacrylic acid molecule. Tertiary butyl hypochlorite (27 g.E0.2S mole) was added slowly to methacrylic acid (43 g.E0.50 mole) containing 0.05 percent p-methoxy phenol. No observable exothermic reaction occurred even when the mixture was heated to 45 C. and held for 20 minutes. This mixture was dis carded.

Tertiary butyl hypochlorite (109.0 g.E1.0 mole) was added slowly to methacrylic acid (86.5 g.E1.0 mole.) containing p-methoxy phenol (0.025 percent) and tetra-' 2.1 methyl ammonium chloride (0.33 gr=-0.003 mole). An immediate, vigorous exothermic reaction occurred. The temperature was maintained at 65 C. until a negative potassium iodide test for the hypochlorite. As in Example XLI, a B sample was prepared by removing the t-butyl alcohol by-product by vacuum distillation.

From analyses similar to those in Example XLI, calculations show that 66 mole percent of the methacrylic acid reacted with itself to form chloro-methacryloxy condensate. The product contains 16 mole percent chlorobutoxy derivative and 16 mole percent vinyl unsaturation.

The liquid B product was homopolymerized using benzoyl peroxide and 65 C. heating. It produced a soft, clear, fairly tough solid.

Example XLIII This example illustrates the preferential haloacylation of methacrylic acid by a second molecule of methacrylic acid in the presence of tetrachloroethylene.

A mixture of tetrachloroethylene (83 g.E0.5 mole) and methacrylic acid (65 g.-="0.75 mole) was prepared containing 0.327 g. (0.003 mole) of tetramethyl ammonium chloride. Tertiary butyl hypochlorite (55 g.z0.50 mole) was added dropwise to this mixture at 25 C. Immediately with the addition of 1-2 grams of t-butyl hypochlorite, the temperature rose to 35 C. This temperature was maintained by ice bath cooling during the addition of the remainder of the hypochlorite. Eighty minutes after the addition of the t-butyl hypochlorite a KI test for I was negative.

Materials volatile at a pot temperature of 62 C. and 12 mm. Hg were removed from a portion of the total reaction mixture by distillation. Chemical analyses of the total reaction mixture and of the residue from the distillation showed that the tetrachloroethylene did not react. The main reaction product was the chloro-methacryloxy condensate derived from the methacrylic acid. Roughly 0.40 mole of the methacrylic acid unsaturation was converted to the chloro-methacryloxy derivative and 0.07 mole to the chloro-butoxy derivative.

A mixture of 4.0 g. of the liquid distillation residue and 0.05 g. of benzoyl peroxide was cast in a mold to form a inch thick sheet. After heating 16 hours at 65 C. and 0.5 hour at 120 C. a clear, hard, brittle resin was obtained.

- Example XLIV Tertiary butyl hypochlorite (76.3 35.50.70 mole) was added slowly to a mixture of allyl chloride (53.5 g.E0.70 mole), methacrylic acid (90.8 g.E1.05 moles), and tetramethyl ammonium chloride (0.23 g.z0.0021 mole). The exothermic reaction was maintained at C. by external cooling. Within 40 minutes a KI test for the hypochlorite was negative.

Materials volatile at 18 mm. Hg and a pot temperature of 65 C. were removed from a portion of the total reaction mixture by distillation. A 69 percent yield of residue product was obtained. Chemical analyses of the total reaction mixture and of the residue product showed that 0.34 mole of chloro-methacryloxy allyl chloride and 0.23 mole of chloro methacryloxy methacrylic acid condensate were the two main products formed.

A mixture of 4.0 g. of the liquid residue product, 2.0 g. of styrene, and 0.50 g. of benzoyl peroxide was heated in a closed mold at 65 C. for 4 hours. A water-clear, hard, brittle solid formed.

Example XLV Tertiary butyl hypochlorite (54.5 g.E0.50 mole) was combined with a mixture of octadecene-l (126.0 g.E0.50 mole), acrylic acid (36.3 g.E0.50 mole), and p-methoxy phenol (0.05 wt. percent of the acrylic acid). The reaction procedure and product isolation outlined in Example XLI was followed. This reaction, however, was slower and took 210 minutes at 65 C.

Calculations, based on the analyses of the A and C samples, showed the formation of 68 mole percent chloroacryloxy octadecane, 10 mole percent chloro-butoxy octa decane, and 22 mole percent chlorinated octadecane-l.

Polymerization of the liquid B sample using 1 percent benzoyl peroxide and 65 C. for 16 hours plus C. for 0.5 hour produced a soft, sticky, rubber-like material.

Example XLVI Tertiary butyl hypochlorite (54.5 g.E0.50 mole) was combined with a mixture of cyclooctene (55 g.E0.50 mole), acrylic acid (36.3 g.E0.50 mole), and p-methoxyphenol (0.05 percent of the acrylic acid). The reaction procedure and product isolation described in Example XLI was followed. This reaction was complete in 50 minutes.

Calculations, based on the analyses of the A and C samples, showed the formation of 70 mole percent chloroacryloxy cyclooctane.

Polymerization of the liquid B sample using 1 percent benzoyl peroxide and 65 C. produced a clear, soft, fair- 1y strong solid which was brittle when rapidly bent.

Example XLVII Tertiary butyl hypochlorite (54.5 g.z0.50 mole) was combined with a mixture of styrene (52050.50 mole). acrylic acid (36.3 g.E0.50 mole), and p-methoxy phenol (0.05 wt. percent of the acrylic acid). The reaction procedure and product isolation described in Example XLI was followed. This reaction was complete within 60 minutes.

Calculations, based on the analyses of the A and C samples, showed the formation of 42 mole percent vicinal chloro-acryloxy ethyl benzene and 34 mole percent vicinal chloro-butoxy ethyl benzene.

Polymerization of the liquid B sample using 1 percent benzoyl peroxide and 65 C. produced a very soft, tacky semi-solid material.

Example XLVIII Tertiary butyl hypochlorite (54.5 g.E0.50 mole) was combined with a mixture of dicyclopentadiene (66.0 g.EO.50 mole), methacrylic acid (43.3 g.E0.50 mole), and p-methoxy phenol 0.05 wt. percent of the methacrylic acid). The reaction procedure and product isolation described in Example XLI was followed. This reaction was complete in 30 minutes.

Calculations, based on the analyses of the A and C samples, showed the formation of 54 mole percent chloromethacryloxy derivative and 14 percent chloro-butoxy derivative of the dicyclopentadiene.

Polymerization of the liquid B sample using 1 percent benzoyl peroxide and 65 C. produced a black, soft, gellike solid.

Example IL A mixture of methacrylic acid (86.5 g.E1.00 mole), p-methoxy phenol (0.0432 .E0.05% of the methacrylic acid), and tertiary butyl hypochlorite (109.0 g.s1.00 mole) was heated to 37 C. in a reaction flask equipped with a stirrer, a gas dispersion inlet tube, a thermometer, and a Dry Ice-methanol cooled condenser. Ethylene (11.0 g.E0.393 mole) was added to the reaction mixture at the rate of 0.073 g./min. The exothermic reaction was controlled at 40-44 C. by ice water bath cooling.

Product isolation was the same as described in Example XLI. The C product isolated after alkaline aqueous washing analyzed as follows:

Acidity, meq./g. 0.02 t-Butyl alcohol, wt. percent 0.5 Total chlorine, meq./ g. 7.69 Allylic chlorine, meq./ g 0.03 Total vinyl, meq./g. 2.67

Saponification, meq./g. 13.34

23 When combined with 1% benzoyl peroxide and heated at 65 C. for 16 hrs., this liquid C product polymerized to a clear, pale yellow, soft extensible, solid.

Example L A mixture of methacrylic acid (86.5 gELOO mole) p-cresol (0.065E0.075% of the methacrylic acid), and t-butyl hypochlorite (109.0 g.E1.00 mole) was heated to 39 C. Propylene (17.3 g.E0.412 mole) was added at the rate of 0.25 g./ min. while controlling the exothermic reaction at 45 C.

Product isolation was the same as described in EX- ample XLI. The C product isolated after alkaline aqueous washings analyzed as follows:

Acidity, meq./g. 0.03 t-Butyl alcohol, wt. percent 0.5

Total chlorine, meq./ g. 7.53 Allylic chlorine, meq./ g. 0.03 Total vinyl, meq./g. 2.38 Saponification, meq./g. 13.16

When combined with 1% benzoyl peroxide and heated at 65 C. for 16 hrs., this liquid C product polymerized to a clear, pale yellow, soft, extensible solid.

Since many embodiments of this invention may be made and since many changes may be made in the embodiments described, the foregoing is to be interpreted as illustrative only, and our invention is defined by the claims appended hereafter.

I claim:

1. The process of preparing a polymerizable long chain compound, which comprises reacting at a temperature of from C. to 100 C. an ethylenically un saturated compound having the structure wherein is an open chain of from to 24 carbon atoms and R is selected from the group consisting of hydrogen and a monovalent aliphatic group, a tertiary alkyl hypochlorite and an acid acrylic compound having the structure wherein R is selected from the group consisting of hydrogen and 0 II COY when R is a hydrogen, R is selected from the group R is selected from the group consisting of hydrogen, halogen and alkyl of from 1 to 4 carbon atoms; and Y is selected from the group consisting of a monovalent aliphatic group of from 1 to 18 carbon atoms and a monovalent aromatic group of from 6 to 18 carbon atoms.

2. The product made by the process of claim 1.

3. The process of claim 1 wherein the acid acrylic compound is a half-ester of an alpha, beta-ethylenically unstaurated dicarboxylic acid.

4. The process of claim 1 wherein the acid acrylic compound is an alpha, beta-ethylenically unsaturated monocarboxylic acid.

5. The product made by the process of claim 3.

6. The product made by the process of claim 4.

7. The process of preparing a polymerizable long chain compound, which comprises reacting at a temperature of from 0 C. to C. an ethylenically unsaturated compound having the structure I RCHzCHCHCH -R is an open chain of from 10 to 24 carbon atoms and R is selected from the group consisting of hydrogen and a monovalent aliphatic group, tertiary butyl hypochlorite and an acid acrylic compound having the structure I II R;O=C=R2-COH wherein R is selected from the group consisting of hydrogen and 0 II -ooY when R is hydrogen, R is selected from the group consisting of hydrogen, alkyl of from 1 to 4 carbon atoms, alkoxy of from 1 to 4 carbon atoms, halogen, phenyl, benzyl and O l -C-H2CH)-OY; when Br is OY R is selected from the group consisting of hydrogen, halogen and alkyl of from 1 to 4 carbon atoms; and Y is selected from the group consisting of a monovalent aliphatic group of from 1 to 18 carbon atoms and a monovalent aromatic group of from 6 to 18 carbon atoms.

8. The process of claim 7 wherein the acid acrylic compound is an alkyl half-ester of maleic acid.

9. The process of claim 7 wherein the acid acrylic compound is an alkyl half-ester of itaconic acid.

10. The process of claim 7 wherein the acid acrylic compound is methacrylic acid.

11. The process of claim 7 wherein the acid acrylic compound is CH CH-COOH.

12. The process of claim 7 wherein the ethylenically unsaturated compound contains a carboxylate group.

13. The process of claim 12 wherein the ethylenically unsaturated compound is a glyceride oil.

14. The product made by the process of claim 13.

15. The process of claim 13 wherein the glyceride oil is linseed oil.

16. The process of claim 13 wherein the glyceride oil is soybean oil.

17. The process of claim 12 wherein the ethylenically unsaturated compound is a tall oil ester.

18. The process of claim 7 wherein the acid acrylic compound is an alkyl half-ester of fumaric acid.

19. The process of claim 18 wherein the acid acrylic compound is a methylamyl half-ester of fumaric acid.

20. The process of claim 18 wherein the acid acrylic compound is an isopropyl half-ester of fumaric acid.

21 The process of claim 18 wherein the acid acrylic compound is a Z-ethylhexyl half-ester of fumaric acid.

22. The process of preparing a polymerizable compound, which comprises reacting an ethylenically unsaturated compound at a temperature of from 50 C. to

C. with a tertiary alkyl hypochlorite and an acid acrylic compound having the structure 0 I I II -o=c-oorr 25 26. The process of preparing a polymerizable long chain compound which comprises reacting an ethylenically unsaturated compound having the structure is an open chain of from 10 to 24 carbon atoms and R is selected from the group consisting of hydrogen and a monovalent aliphatic group, a tertiary butyl hypochlorite and an acid acrylic compound having the structure at a temperature of from 50 C. to 150 C.

27. The process of preparing a polymerizable compound, which comprises reacting substantially equal molar quantities of maleic anhydride and monohydroxy compound having the structure YOH wherein Y is selected from the group consisting of a monovalent aliphatic group of from one to eighteen carbon atoms and a monovalent aromatic group of from six to eighteen carbon atoms at a temperature of from about 20 C. to 200 C. whereby a maleic acid half-ester is formed, isomerizing said maleic acid half-ester at a tempertaure of from about 50 C. to 200 C. in the presence of an isomerization catalyst to form a fumaric acid half-ester, and then reacting a glyceride oil with said fumaric acid half-ester and tertiary butyl hypochlorite at a temperature of from C. to 100 C.

28. The process of preparing a polymerizable compound which comprises reacting maleic anhydride and a mono-hydroxy organic compound having the structure YOH, wherein Y is selected from the group consisting of a monovalent aliphatic group of from one to eighteen carbon atoms and a monovalent aromatic group of from six to eighteen carbon atoms, whereby a maleic acid half-ester is formed, isomerizing said maleic acid halfester to form a fumaric acid half-ester, and then reacting an ethylenically unsaturated compound having an ethylenically unsaturated open chain of from to 24 car- 26 bon atoms with said fumaric acid half-ester and a tertiary butyl hypochlorite at a temperature of from C. to C., said ethylenically unsaturated compound having the structure RCH CH=CH-CH R wherein R is selected from the group consisting of hydrogen and a monovalent aliphatic group.

29. The process of preparing a polymerizable compound which comprises reacting maleic anhydride and a monohydroxy organic compound having the structure YOH, wherein Y is selected from the group consisting of a monovalent aliphatic group of from one to eighteen carbon atoms and a monovalent aromatic group of from six to eighteen carbon atoms, whereby a maleic acid halfester is formed, isomerizing said maleic acid half-ester to form a fumaric acid half-ester, and then reacting an ethylentically unsaturated compound with said fumaric acid half-ester and a tertiary butyl hypochlorite at a temperature of 50 C. to 150 C.

30. The process of preparing a polymerizable compound which comprises reacting an ethylenically unsaturated compound at a temperature of from 50 C. to 150 C. with tertiary butyl hypochlorite and an acid acrylic compound having the structure 0 =C ('lOH References Cited by the Examiner UNITED STATES PATENTS 2,054,814 9/1936 Harford 260-469 2,511,870 6/1950 Oroshnik 260497 2,514,672 7/1950 Reynolds et a1. 260-484 2,728,781 12/1955 Shokal et a1. 26018 2,947,766 8/1960 Riener 260405 3,010,925 11/1961 Lynn 26063 CHARLES E. PARKER, Primary Examiner.

LEON I. BERCOVITZ, JOSEPH P. BRUST,

Examiners.

RONALD W. GRIFFIN, ANTON H. SUTTO,

Assistant Examiners. 

1. THE PROCESS OF PREPARING A POLYMERIZABLE LONG CHAIN COMPOUND, WHICH COMPRISES REACTING AT A TEMPERATURE OF FROM 0*C. TO 100*C. AN ETHYLENICALLY UNSATURATED COMPOUND HAVING THE STRUCTURE 